Ethyl 2,2-dimethyl-3(di(2-methoxyethyl) amino)carbonylcyclobutaneacetate

ABSTRACT

ETHYL 2,2 - DIMETHYL(DI(2 - METHOXYETHYL)AMINO)CARBONYLCYCLOBUTANEACETATE, USEFUL AS A PRIMARY PLASTICIZER, HAS BEEN PREPARED.

United States Patent Int. Cl. C07c 103/86 US. Cl. 260-468 1 ClaimABSTRACT OF THE DISCLOSURE Ethyl 2,2 dimethyl[di(2methoxyethyl)amino]carbonylcyclobutaneacetate, useful as a primaryplasticizer, has been prepared.

This application is a division of application bearing Ser. No. 632,464,filed Dec. 16, 1966, now Pat. No. 3,519,661, which, in turn, is adivision of application bearing Ser. No. 392,354, filed Aug. 26, 1964,now Pat. No. 3,309,333.

A nonexclusive, irrevocable, royalty-free license in the inventionherein described, throughout the World for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

This invention relates to N,N-disubstituted amides. More specifically,it relates to N,N-disubstituted amides useful as primary plasticizersfor hydrophobic and hydrophilic resins. Still more specifically, itrelates to vinyltype resin compositions comprising the N,N-disubstitutedamide plasticizers. These plasticizers are characterized by their greatefficiency as compatible plasticizers for polyvinyl chloride polymersand copolymer imparting dairable low temperature properties and lowvolatility loss to the plasticized resin.

A primary object of the present invention is to provide for vinyl-typehydrophobic resins a group of primary plasticizers that are highlycompatible with and do not exude from these resins.

Another object is to employ as these plasticizers certain novelN,N-disubstituted amides. Still another object is to prepare theseN,N-disubstituted amides from commercially-available chemicals usingcommercially-available equipment. A still further object is to provide aplasticized vinyl-type polymer or copolymer comprising theseplasticizers, These and other objects will be discussed more fullybelow.

The N,N-disubstituted amides may be represented by the formula (C112)RCN (Gum-X wherein:

(a) R i is an acyl group having from 8 to 22 carbon atoms and may besaturated, unsaturated, normal, branched,

3,584,039 Patented June 8, 1971 ice epoxy, aliphatic, cyclic, alicyclic,naphthenic, terpenic, terpene-derived, and mixtures thereof,

(b) n is an integer equal to at least one but less than five, that is,from "1 to 4, inclusive, and

(c) X is a member selected from the group consisting of OR, COOR, CN,O(CH ON, and

O (CH COOR' wherein R is an alkyl group containing from one to eightcarbon atoms, and m is an integer from 1 to 2 inclusive.

In another embodiment of this invention X is selected from the group-halogen ll ---0 P-(O R)z, and

wherein R is an alkyl group containing from 1 to 8 carbon atoms.

Among the operable N,N-disubstituted amides of this invention arecompounds of the above general formula in which the acyl group is anacyl such as the acyls of the following types of acids; monobasic anddibasic normal or branched chain alkanoic and alkenoic acids withsubstituents in the chain such as; dichlorostearic acid; monoordihydrostearic acids; acyloxyacids such as 12-acetoxyoleic,12-acetoxystearic, 9,10-diacetoxystearic, and acylated recinoleic acidsand the like; IZ-beta-cyanoethoxyoleic and 12-cyanoethoxystearic acidsand the like; ricinoleic acid; phenylstearic acid; phenoxystearic acid;mono-, di-, or tri-epoxy stearic acids; monoor diepoxy oleic acid;epoxydocosanoic acid; dimerized or trimerized linolenic, linoleic, oroleic acid; etc.; cyclic or alicyclic acids such as cyclized linoleicand/or linolenic acids; Diels-Alder adducts of such individual or mixedpolyenoic acids as can be derived from tung oil acids or soybean acids;the Diels- Alder adducts of individual or mixed tung oil acids withdi-alkyl maleates, alkyl acrylates, acrylonitrile, fumaronitrile and thelike; tall oil acids; rosin-derived or terpenederived acids such asabietic, l-pimaric, pinonic and the gamma-lactone ofbeta-hydroxyisopropyl pimelic acid; as well as the mono-alkyl esters ofdibasic acids such as the monobutyl esters of pinic, adipic, sebacic,azelaic, brassylic, carboxystearic, phthalic, and terephthalic acids, orof phosphonated fatty acids such as dialkyl phosphonostearic acid, andthe like.

Also included among the operable N-acyl compounds of this invention arethe corresponding N,N-disubstituted amides of normal, branched,aliphatic, alicyclic, or aromatic dibasic acids such as adipic, sebacic,azelaic, brassylic, carboxystearic, dimer, trimer, pinic, phthalic, andterephthalic acids. Other useful binary, ternary or multiple componentmixtures of amides of saturated, monounsaturated, and polyunsaturatedacids are the N,N-

disubstituted amides of synthetic mixtures of fatty acids which can beobtained from such natural sources as white greases, menhaden oil,jojoba oil, parsley seed oil, rapeseed oil, crambe seed oil, cottonseedoil, soybean oil, Limanlhes douglasii seed oil, palm oil, Vernoniaanthelmintica seed oil, castor oil, and other seed oils; or from foots,tall-oil acids or rosin acids.

As used herein, the term dimer acid or dimerized acid relates to acidsor mixtures of acids consisting essentially of dibasic acids containingfrom 32 to 44 carbon atoms resulting from polymerization or dimerizationof long chain C to C unsaturated fatty acids. The term trimer acid, ortrimerized acids relates to acids or mixtures of acids consistingessentially of tribasic acids containing from 48 to 66 carbon atomsresulting from the polymerization or trimerization of long chain C to Cunsaturated fatty acids. These products are commercially available.

Specific examples of the N,N-disubstituted amides described above are:

N,N-bis 2-methoxyethyl) oleamide N,N-bis (2-ethoxyethyl oleamideN,N-bis(2-ethoxyethyl)palmitamide N,N-bis (2-ethoxyethyl)2-ethylhexanamide N,N-bis(2-ethoxyethyl)napthenamide Ethyl2,2-dimethyl-3 [di (2-methoxyethyl) amino] carbonylcyclobutaneacetateN,N-bis(2-methoxyethyl)amide of hydrogenated cottonseed oil fatty acidsN,N-bis(2-ethoxyethyl)amide of animal acidsN,N-bis(2-cyanoethyl)oleamide N,N-bis(2-ethoxyethyl)decanamide N,N-bis(2-ethoxyethyl) stearamide N,N-bis 2-ethoxyethyl) erucamideN,N-bis(2-ethoxyethyl)amide of Limantlzes douglasii oil fatty acidsN,N,N,N'-Tetra(2-ethoxyethyl)amide of dimer acidN,N-bis(2-methoxyethyl)amide of parsley seed oil fatty acidsN,N-bis(2-methoxyethyl)amide of rapeseed oil fatty acids N,N-bisZ-methoxyethyl) linoleamide N,N-bis(2-ethoxyethyl)epoxystearamideN,N-bis 2-cyanoethoxyethyl) oleamide N,N-bis(carbethoxymethyl)oleamideIt is an advantage of our invention that the N,N- disubstituted amidesare excellent primary, solvent-type plasticizers for vinyl-type resins.As used herein, the term primary, solvent-type plasticizer relates to acompound which is compatible when used alone. The term vinyl type resinincludes the hydrophobic polymers and copolymers of monomers containingvinyl chloride in major proportions by weight.

It is a further advantage of our invention that the N,N- disubstitutedamides are compatible, solvent-type plasticizers for the vinyl-typeresins. As used herein, the terms compatible, good compatibility, andcompatible plasticizers refer to plasticizers which show no sign ofexudation or migration to the surface for at least two weeks duringshelf storage, when the plasticizers are present in the hydrophobicresin in proportions of about 70 parts of plasticizer per 100 parts ofresin, parts being by weight. When a resin is plasticized with acompound with which it has only limited compatibility, the plasticizersoon exudes or migrates to the surface unless the plasticizer is usedeither in a limited amount or is used in conjunction with a mutualsolvent (a compatible auxiliary plasticizer) to obtain adequatecompatibility.

It is a still further advantage of this invention that the efiicient,primary, solvent-type plasticizers may be made fromcommercially-available, low-price fatty acids usingcommercially-available equipment. Most important these novelplasticizers for vinyl-type resins are characterized by excellentlow-temperature properties, i.e., they prevent the resin compositionfrom becoming brittle or from cracking at sub-zero centigradetemperatures.

These N,N-disubstituted amides may also be used as softeners for nitrilerubber, e.g. Tycar 1042 (33% acrylonitrile).

These and other advantages will be apparent to those skilled in the art.

The compounds that are the subject of this invention are convenientlyprepared by reacting the appropriate amine with the appropriate acid, orcorresponding acid chloride. In any event, methods for preparingcompounds such as those described herein are Well known to those skilledin the art or fatty acid chemistry. The details of individualpreparations are listed in the following operating examples. Theseexamples are set forth by way of illustration and it will be understoodthat the invention is not to be construed as limited to these compoundsor by the details therein. Analyses are in weight percent.

EXAMPLE 1 N,N-bis 2-methoxyethy1) oleamide A mixture of 31.2 grams (0.23mole) of di(2-methoxyethyl)amine, 40 grams (0.14 mole) of oleic acid,and 20 milliliters of benzene is refluxed in an apparatus equipped witha Dean-Stark trap until the evolution of water ceases. The reactionmixture is diluted with 150 milliliters of commercial hexane, Washedsuccessively With dilute hydrochloric acid and water, and dried overanhydrous sodium sulfate. Free acid is removed by percolating the hexanesolution through a column of activated alumina, and eluting the amidewith a 1:1 hexane-ethanol mixture. The solvent is removed by strippingunder reduced pressure. Analysis of the product,N,N-bis(2-methoxylethyl) oleamide: C, 72.18% (theory 72.43); H, 11.75%(theory 11.92); N, 3.53% (theory 3.52).

EXAMPLE 2 N,N-bis (2-ethoxyethyl)palmitamideN,N-bis(2-ethoxyethyl)palmitamide is prepared by the procedure ofExample 1 from 30.2 grams (0.19 mole) of di(2-ethoxyethyl)amine and 40grams (0.16 mole) palmitic acid. Analysis of the product,N,N-bis(2-ethoxyethyl)palmitamide: C, 71.89% (theory 70.34); H, 12.43%(theory 12.06); N, 3.50% (theory 3.51).

EXAMPLE 3 N,N-bis( Z-ethoxyethyl) ole amideN,N-bis(2-ethoxyethyl)oleamide is prepared by the procedure of Example 1from 33.8 grams (0.21) mole of d1(2-ethoxyethyl)amine and 40 grams (0.14mole) of oleic acid. Analysis of the product, N,N-bis(2.-ethoxyethyl)oleamide: C, 73.37% (theory 73.31); H, 11.75% (theory 11.92); N,3.53% (theory 3.52).

EXAMPLE 4 N,N-bis (2-ethoxyethyl)-2-ethylhexanamide This product isprepared using 30.2 gr. (0.20 mole) of d1(2-et1hoxymethyl)amine, 15.8grams (0.20 mole) of pyridine dissolved in milliliters of benzene, and30.5 grams (0.20 mole) of Z-ethylhexanoyl chloride which is addeddropwise with stirring. After stirring for an additional hour thereaction mixture is filtered, washed successrvely with dilutehydrochloric acid and water, and dried over anhydrous sodium sulfate.Free acid is removed by percolating the benzene solution through acolumn of activated alumina and eluting the amide with a 1:1ethanol-benzene mixture. The solvent is then removed by strlpping underreduced pressure. Analysis of the product,N,N-bis(Z-ethoxyethyl-Z-ethylhexanamide: C, 66.26 per cent (theory66.85); H, 11.65 percent (theory 11.56); N, 4.88 percent (theory 4.80).

EXAMPLE 5 N,N-bis(2-ethoxyethyl) naphthenarnideN,N-bis(2-ethoxyethyl)naphthenamide is prepared by the procedure ofExample 1 from 29.3 grams (0.18 mole) of di(2-ethoxyethyl)amine and 30grams (0.14 mole) of naphthenic acid. The neutralization equivalent ofthe naphthenic acid is 217. The product,N,N-bis(2-ethoxyethyl)naphthenamide, has a nitrogen content of 3.90%(theory 3.89).

EXAMPLE 6 Ethyl 2,2-dimethyl-3 [di 2-methoxyethyl) amino]carbonylcyclobutaneacetate This material is prepared by the procedure ofExample 4 from 17.2 grams (0.13 mole) of di(2-methoxyethyl) amine, 30grams (0.13 mole) of ethyl 2,2-dimethyl-3-chlorocarbonylcyclobutaneacetate, and 10.2 grams (0.13 mole) ofpyridine. Analysis of the product, ethyl 2,2-dimethyl 3[di(2methoxyethyl)amino]carbonylcyclobutaneacetate: C, 61.15% (theory 62.01);H, 9.56%

(theory 9.50); N, 4.09% (theory 4.25).

EXAMPLE 7 N,N-bis(2-methoxyethyl)amide of selectively hydrogenatedcottonseed oil fatty acids N,N-bis(2-methoxyethyl)amide of selectivelyhydrogenated cottonseed oil fatty acids are prepared by the procedure ofExample 1 from 25.5 grams (0.19 mole) of di(2-methoxyethyl)amine and 35grams (0.12 mole) of selectively hydrogenated cotonseed oil fatty acids.(The selectively hydrogenated cottonseed oil fatty acids have an iodinevalue of 73.2, a thiocyanogen value of 68.0, and a neutralizationequivalent of 274.) The product, N,N-bis- (2-methoxyethyl)amide ofselectively hydrogenated cottonseed oil fatty acids, has a nitrogencontent of 3.63%

EXAMPLE 8 N,N-bis(2-ethoxyethyl)amide of animal acidsN,N-bis(2-ethoxyethyl)amide of animal acids (Neofat No. 65) is preparedby the procedure of Example 1 from 43.9 grams (0.27 mole) ofdi(2-ethoxyethyl)amine and 50 grams (0.19 mole) of Neofat No. 65, acommercial product which is a mixture of fatty acids having thefollowing composition: 2% myristic, 26% Palmitic, 16% stearic, 48%oleic, and 8% linoleic acids. The resulting product,N,N-bis(2-ethoxyethyl)amide of animal acids, has a nitrogen content of3.33% (theory 3.36).

EXAMPLE 9 N,N-bis (carbethoxymethyl) oleamideN,N-bis(carbethoxymethyl)oleamide is prepared by the procedure ofExample 4 from 18.9 grams (0.10 mole) of di(carbethoxymethyl)amine, 31.5grams (0.10 mole) of oleoyl chloride, and 8.1 grams (0.10 mole) ofpyridine. The product, N,N-bis(carbethoxymethyl)oleamide has a nitrogencontent of 2.97% (theory 3.09%

EXAMPLE 1O N,N-bis (2-ethoxyethyl) decanamideN,N-bis(2-ethoxyethyl)decanamide is prepared by the procedure of Example1 from 47.1 grams (0.29 mole) of di(2-ethoxyethyl)amine and 35 grams(0.20 mole) of capric acid. Analysis of the product,N,N-bis(2-ethoxyethyl)decanamide: C, 67.97% (theory 68.51); "H, 11.66%(theory 11.83); N, 4.42% (theory 4.44).

EXAMPLE 1 1 N,N-bis(2-ethoxyethy1)stearamideN,N-bis(2-ethoxyethyl)stearamide is prepared by the procedure of Example1 from 29.7 grams 0.18 mol of di(2-ethoxyethyl)amine and 35 grams (0.12mole) of stearic acid. Analysis of the product, N,N-bis(2-ethoxy-EXAMPLE 13 N,N-bis(2-ethoxyethyl)amide of Limnavzthes douglasii oilfatty acids N,N-bis(2-ethoxyethyl)amide of Limnanthes douglasz'i oilfatty acids is prepared by the procedure of Example 1 from 26.4 grams(0.16 mole) of di(2-ethoxyethyl)amine and 35 grams (0.11 mole) of Limnanthes douglasii oil fatty acids. (The Limnamhes douglasii oil fattyacids has a neutralization equivalent of 320.) The product N,N-bis-(2-ethoxyethyl)amide of Limanthes douglasii oil fatty acids has anitrogen content of 3.09%.

EXAMPLE 14 N,N-N',N'-tetra(2-ethoxyethyl)amide of dimer acid Thismaterial is prepared by the procedure of Example 1 from 30.1 grams (0.19mole) of di(2-ethoxyethyl)amine and 35 grams (0.06 mole) of dimer acid.The resulting product has a nitrogen content of 2.91%

EXAMPLE 15 N,N-bis(2-methoxyethyl)amide of parsley seed oil fatty acidsN,N-bis(2-methoxyethyl)amide of parsley seed oil fatty acids is preparedby the procedure of Example 1 from 32.6 grams (0.25 mole) ofdi(2-methoxyethyl)amine and 50 grams (0.16 mole) of parsley seed oilfatty acids. The resulting product has a nitrogen content of 2.99%(theory 3.22).

EXAMPLE 16 N,N-bis(2-methoxyethyl) amide of rapeseed oil fatty acidsThis material is prepared by the procedure of Example 1 using 32.9 grams(0.25 mole) of di(Z-methoxyethyl) amine and 50 grams (0.16 mole) ofrapeseed oil fatty acids. The resulting product has a nitrogen contentof 3.10% (theory 3.35).

EXAMPLE 17 N,N-bis(2-methoxyethyl)linoleamide This material is preparedby the procedure of Example 1 from 28.5 grams (0.21 mole) ofdi(2-methoxyethyl) amine and 40 grams (0.14 mole) of linoleic acid.Results of the analysis of the resulting product follow: C, 72,48percent (theory 72.83); H, 11.43 percent (theory 11.38); N, 3.48 percent(theory 3.54).

EXAMPLE 18 N,N-bis(2ethoxyethyl)epoxystearamideN,N-bis(2-ethoxyethyl)epoxystearamide is an epoxidized sample of theN,N-bis(22-ethoxyethyl)oleamide of Example 3, having an oxirane oxygencontent of 3.33%.

EXAMPLE 19- N,N-bis (2-cyanoethyl)oleamide N,N-bis(2-cyanoethyl)oleamidewas prepared by the procedure of Example 4 from 14.3 grams (0.12 mole)of 5- 3-iminodipropionitri1e, 35 grams (0.12 mole) of oleoyl chloride,and 9.2 grams (0.12 mole) of pyridine. Analysis of the resulting productgives: C, 73.69 percent (theory 74.36); H, 10.63 percent (theory 10.66);N, 10.80 (theory 10.85).

EXAMPLE N,N-bis (Z-cyanoethoxyethyl oleamide Fifty grams (0.135 mole) ofN,N-bis(2-hydroxyethyl) oleamide, and 5 ml. of Triton B in methanol) in5 ml. of water are dissolved in an equal volume of 1,4-dioxane. Thetemperature is then raised to C. after which 29 grams (0.55 mole) ofacrylonitrile is added dropWise with stirring. Stirring is thencontinued for about three hours after the acrylonitrile addition. Whilestill warm the reaction mixture is poured into 800 milliliters ofdiethyl ether, and allowed to stand overnight. The polyacrylonitrile isthen filtered off and the filtrate washed successively with four 50-ml.portions of normal hydrochloric acid in water, dried, and stripped ofsolvent. The residual acidity is removed by percolation throughactivated alumina. The resultant product has a nitrogen content of 8.50%(theory 8.80%).

Portions of the products prepared according to Examples 1 through 20 arethen evaluated as primary, sol- Percent Polymer (or copolymer) 63.5Plasticizer 35.0 Stearic acid 0.5 Basic lead carbonate 1.0

Total 100.0

TABLE I Vola- Tenslle Elonga- Brittle tility Exampm strength, modulus,tion, point, loss, Compati- Number m ti p.s.1. p.s.1. percent percentbility 1 N,N-bis(2-methoxyethyl)oleamide 2, 800 1, 370 53 2. 70 C 2N,N-bis(2-ethoxyethyl)palmrtamrde.. 2, 860 1, 390 360 43 1. 21 0 3N,N-bis(Z-ethoxyethyDoleamrde 2, 800 1, 410 340 57 2. 01 0 4N,N-bis(2-ethoxyethyl) 2-ethylhexanamide 2, 760 1, 280 320 -37 8. 23

5 N,N-bis(2-ethoxyethyl)naphthenamide 3, 050 1, 600 300 21 9. 58 c 6Ethyl 2,2-dimethy1-3[dl(z-methoxyethyl)am1no]carb0nyl- 3, 300 1, 510 3107 7. 55 0 cyclobutaneacetate.

7 N ,N-bis(2-methoxyethyDamide of selectively hydrogenated 2, 630 1, 310300 49 1 13 0 cottonseed oil fatty acids.

3 N,N -bis(2-ethoxyethyl)a.m1de of annual acids 2, 790 1, 440 340 47 1.40 G N,N-bis(carbethoxymethyl)oleamide 2, 9 0 1, 720 280 33 CN,N-bis(Z-ethoxyethyl)deeanamide. 2, 580 1, 090 350 45 7. 33 CN,N-bis(2-ethoxyethyl)stearamrde. 2, 820 1, 470 360 37 0. 82 ON,N-bis(Z-ethoxyethyDerucamide 2, 480 1, 630 270 -51 0. 83 C N,I I-)is(2-ethoxyethyl)amide of Limnathes douglasiz oil fatty 3, 280 1, 560330 45 1. 51 0 am s. N,N- ,N-tetra(2-ethoxyethyl) amide of dimer acid 3,120 2, 076 320 25 0. 43 C N,N-bis(2-methoxyethyl)amide of parsley seed011 fatty acids- 2, 910 1, 850 360 47 1. 94 CN,N-bis(2-meth0xyethyl)amide of rapeseed O11 fatty acids 2, 880 1, 440380 51 0. 83 G N,N-bis (Z-methQXyethyDIiHOleam' 8 860 440 350 IN,N-bis(2-ethox N,N-

20 N,N-bis(2-cy anoethoxyethyDoleamide Di-Z-ethylhex Dioctyl adipate(control N01E.Above compounds tested in vinyl-chlorlde-vinyl acetatecopolymer. Compound 2a tested in polyvinyl chloride.

is used, percent being by weight.

We claim: 1. Ethyl2,2-dimethyl-3[di(2-methoxyethyl)amino]carbonylcyclobutaneacetate.

References Cited Lewis et al., J.O.C. 24, 1870, 1959.

LORRAINE A. WEINBERGER, Primary Examiner 0 R. GERSTL, Assistant Examiner

